Theoretical investigation of the intermediate structures of catalytic cycles by the multi configurational theories

• Project/Area Number: 25410030
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Physical chemistry
• Research Institution: Institute for Molecular Science
• Principal Investigator: KURASHIGE Yuki 分子科学研究所, 理論・計算分子科学研究領域, 助教 (30510242)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2015: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2014: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 電子状態理論 / 遷移金属錯体 / 金属酵素 / 量子化学計算 / 多参照理論 / 金属錯体 / EPR / 電子相関理論 / 密度行列繰り込み群 / 水分解反応 / 多参照電子相関理論

Outline of Final Research Achievements

This study revealed many electronic properties, such as oxidation states and spin states of the metalloenzymes, which are directly associated with the mechanism of the catalytic reaction. We also revealed rich information contained in the wavefunctions on the catalytic ability of the cluster through an analysis for quantum entropy along the catalytic cycle. The results have brought us one step closer understanding how multi-nuclear complexes exhibit exceptional catalytic ability in metalloenzymes.

Research Products

• [Journal Article] A pentanuclear iron catalyst designed for water oxidation (2016)
  • Author(s): Masaya Okamura, Mio Kondo, Reiko Kuga, Yuki Kurashige, Takeshi Yanai, Shinya Hayami, Vijayendran K. K. Praneeth, Masaki Yoshida, Ko Yoneda, Satoshi Kawata, and Shigeyuki Masaoka
  • Journal Title: Nature Volume: 530 Issue: 7591 Pages: 465-468
  • DOI: 10.1038/nature16529
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Multinuclear Metal-Binding Ability of a Carotene (2015)
  • Author(s): T. Murahashi et al.
  • Journal Title: Nature Communications Volume: 6 Issue: 1 Pages: 6742-6749
  • DOI: 10.1038/ncomms7742
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Aggregation-Induced Photon Upconversion through Control of the Triplet Energy Landscapes of the Solution and Solid States (2015)
  • Author(s): Pengfei Duan, Nobuhiro Yanai, Yuki Kurashige, and Nobuo Kimizuka
  • Journal Title: Angew. Chem. Int. Ed. Volume: 54 Issue: 26 Pages: 7544-7549
  • DOI: 10.1002/anie.201501449
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Fully internally contracted multireference configuration interaction theory using density matrix renormalization group: A reduced-scaling implementation derived by computer-aided tensor factorization (2015)
  • Author(s): M. Saitow, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: 11 Issue: 11 Pages: 5120-5131
  • DOI: 10.1021/acs.jctc.5b00270
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Acid/Base-Regulated Reversible Electron Transfer Disproportionation of N-N linked Bicarbazole and Biacridine Derivatives (2015)
  • Author(s): Palash Pandit,† Koji Yamamoto,† (†: equally contributed) Toshikazu Nakamura, Katsuyuki Nishimura, Yuki Kurashige, Takeshi Yanai, Go Nakamura, Shigeyuki Masaoka, Ko Furukawa, Yumi Yakiyama, Masaki Kawano and Shuhei Higashibayashi
  • Journal Title: Chemical Science Volume: 印刷中 Issue: 7 Pages: 4160-4173
  • DOI: 10.1039/c5sc00946d
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Synthesis of Molecular Wires Strapped by π-Conjugated Side Chains: Integration of Dehydrobenzo[20]annulene Units (2015)
  • Author(s): J. Terao, M. Ohsawa, H. Masai, Y. Kurashige, T. Fujihara, and Y. Tsuji
  • Journal Title: J. Org. Chem. Volume: 80 Issue: 17 Pages: 8874-8880
  • DOI: 10.1021/acs.joc.5b01414
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Modulation of benzene or naphthalene binding to palladium cluster sites by the backside-ligand effect (2015)
  • Author(s): Y. Ishikawa, S. Kimura, K. Takase, K. Yamamoto, Y. Kurashige, T. Yanai, T. Murahashi
  • Journal Title: Angewandte Chemie International Edition Volume: 54 Issue: 8 Pages: 2482-2486
  • DOI: 10.1002/ange.201409499
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Scalar relativistic calculations of hyperfine coupling constants using ab initio density matrix renormalization group method in combination with third-order Douglas-Kroll-Hess transformation: case studies of 4d transition metals (2015)
  • Author(s): T. N. Lan, Y. Kurashige, and T. Yanai
  • Journal Title: J. Chem. Theo. Comp. Volume: 11 Issue: 1 Pages: 73-81
  • DOI: 10.1021/ct5007778
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Density matrix renormalization group for ab initio Calculations and associated dynamic correlation methods: A review of theory and applications (2015)
  • Author(s): T. Yanai, Y. Kurashige, J. Chalupsky, T. N. Lan, and M. Saitow
  • Journal Title: Int. J. Quantum Chem. Volume: 115 Issue: 5 Pages: 283-299
  • DOI: 10.1002/qua.24808
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Complete active space second-order perturbation theory with cumulant approximation for large entanglement space from density matrix renormalization group (2014)
  • Author(s): Y. Kurashige, J. Chalupsky, T. N. Lan, and T. Yanai
  • Journal Title: J. Chem. Phys. Volume: 141 Issue: 17
  • DOI: 10.1063/1.4900878
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Reactivity of Binuclear Non-Heme Iron Δ9 Desaturase Studied by Large-scale Multireference Ab Initio Calculations (2014)
  • Author(s): J. Chalupsky, T. A. Rokob, Y. Kurashige, T. Yanai, E. I. Solomon, L. Rulisek, and M. Srnec
  • Journal Title: J. Am. Chem. Soc, Volume: 136 Issue: 45 Pages: 15977-15991
  • DOI: 10.1021/ja506934k
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Theoretical study of the π→π* excited states of oligoacenes: a full π-valance DMRG-CASPT2 study (2014)
  • Author(s): Y. Kurashige and T. Yanai
  • Journal Title: Bull. Chem. Soc. Jpn Volume: 87 Issue: 10 Pages: 1071-1073
  • DOI: 10.1246/bcsj.20140180
  • NAID: 130004153323
  • Peer Reviewed / Open Access / Acknowledgement Compliant
• [Journal Article] Ab Initio Density Matrix Renormalization Group Study of Magnetic Coupling in Dinuclear Iron and Chromium Complexes (2014)
  • Author(s): T. V. Harris, Y. Kurashige, T. Yanai, and K. Morokuma,
  • Journal Title: The Journal of Chemical Physics Volume: 140 Issue: 5
  • DOI: 10.1063/1.4863345
  • Peer Reviewed
• [Journal Article] Toward reliable prediction of hyperfine coupling constants using ab initio density matrix renormalization group method: diatomic radicals as test cases (2014)
  • Author(s): L. N. Tran, Y. Kurashige, and T. Yanai
  • Journal Title: Journal of Chemical Theory and Computation Volume: - Issue: 5 Pages: 1953-1967
  • DOI: 10.1021/ct400978j
  • Peer Reviewed
• [Journal Article] Radical O-O coupling reaction in diferrate-mediated water oxidation studied with multireference wave function theory (2014)
  • Author(s): Y. Kurashige, M. Saitow, J. Chalupsky; and T. Yanai
  • Journal Title: Physical Chemistry Chemical Physics Volume: - Issue: 24 Pages: 11988-11999
  • DOI: 10.1039/c3cp55225j
  • Peer Reviewed
• [Journal Article] Entangled quantum electronic wavefunctions of the Mn4Ca cluster in photosystem II (2013)
  • Author(s): Y. Kurashige, G. K-L. Chan, and T. Yanai
  • Journal Title: Nature Chemistry Volume: 5 Issue: 8 Pages: 660-666
  • DOI: 10.1038/nchem.1677
  • Peer Reviewed
• [Journal Article] Highly scalable multireference configuration interaction theory with internal contraction of density matrix renormalization group wave function (2013)
  • Author(s): M. Saitow, Y. Kurashige, and T. Yanai
  • Journal Title: The Journal of Chemical Physics Volume: 139 Issue: 4
  • DOI: 10.1063/1.4816627
  • Peer Reviewed
• [Journal Article] Multireference Ab Initio Density Matrix Renormalization Group (DMRG)-CASSCF and -CASPT2 Study on the Photochromic Ring-Opening of Spiropyran (2013)
  • Author(s): F. Liu, Y, Kurashige, T. Yanai, K. Morokuma
  • Journal Title: J. Chem. Theo. Comp. Volume: 9 Issue: 10 Pages: 44624469-44624469
  • DOI: 10.1021/ct400707k
  • Peer Reviewed
• [Presentation] Applications of DMRG-based multireference correlation theories (2016)
  • Author(s): Y. Kurashige
  • Organizer: 251st ACS National Meeting
  • Place of Presentation: San Diego Convention Center, California, USA
  • Year and Date: 2016-03-13
  • Int'l Joint Research / Invited
• [Presentation] Applications of DMRG-based multireference correlation theories (2015)
  • Author(s): Y. Kurashige
  • Organizer: The 15th International Congress of Quantum Chemistry (ICQC) Satellite
  • Place of Presentation: AICS, Kobe, Hyogo, Japan
  • Year and Date: 2015-06-18
  • Int'l Joint Research / Invited
• [Presentation] Development of Multireference Electronic -Structure Methods and Application to Multinuclear Complexes and Metalloenzymes (2015)
  • Author(s): Yuki Kurashige
  • Organizer: The 95th Annual Meeting of the Chemical Society of Japan
  • Place of Presentation: 千葉県船橋市、日大船橋キャンパス
  • Year and Date: 2015-03-29
  • Invited
• [Presentation] Quantum chemistry meets density matrix renormalization group (DMRG) theory: Theory and applications to π-conjugated systems (2015)
  • Author(s): Yuki Kurashige
  • Organizer: WPI-MANA Seminar
  • Place of Presentation: 茨城県つくば市、MANAセンター
  • Year and Date: 2015-03-19
  • Invited
• [Presentation] 多参照電子状態理論の最近の進展 (2015)
  • Author(s): 倉重佑輝
  • Organizer: 第２９回九州大学CMSセミナー
  • Place of Presentation: 福岡県福岡市、九大伊都キャンパス
  • Year and Date: 2015-01-23
  • Invited
• [Presentation] 多参照電子状態理論によるπ共役分子の励起状態解析 (2014)
  • Author(s): 倉重佑輝
  • Organizer: 「柔らかな分子系」第７回ワークショップ
  • Place of Presentation: 愛知県岡崎市、岡崎CC
  • Year and Date: 2014-12-13
  • Invited
• [Presentation] 有機結晶におけるマルチエキシトン生成機構の理論的解明 (2014)
  • Author(s): 倉重佑輝
  • Organizer: 「柔らかな分子系」第５回ワークショップ
  • Place of Presentation: 広島県広島市、アステールプラザ
  • Year and Date: 2014-09-20
  • Invited
• [Presentation] 分子多参照電子状態 (2014)
  • Author(s): 倉重佑輝
  • Organizer: CMSI「新物質・新量子相の基礎科学」 夏の学校 2014
  • Place of Presentation: 滋賀県高島市、白浜荘
  • Year and Date: 2014-08-21 – 2014-08-22
  • Invited
• [Presentation] 多参照電子相関理論における最近の進展 (2014)
  • Author(s): 倉重佑輝
  • Organizer: スーパーコンピューターワークショップ２０１４
  • Place of Presentation: 愛知県、岡崎コンファレンスセンター
  • Invited
• [Presentation] 多配置電子状態理論を用いた光合成マンガンクラスタおよび人工金属錯体水分解反応の研究 (2014)
  • Author(s): 倉重佑輝、柳井毅
  • Organizer: 異分野融合による新材料開発のための計算科学-光合成マンガンクラスターの理論計算-
  • Place of Presentation: 兵庫県、神戸理研AICS
  • Invited
• [Presentation] 鉄(VI)二核錯体を介した酸素生成反応の理論的研究 (2014)
  • Author(s): 倉重佑輝、斎藤雅明、J. Chalupsky、柳井毅
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 愛知県、名古屋大学東山キャンパス
• [Presentation] 光合成系IIマンガンクラスタの電子構造に関する理論的研究 (2013)
  • Author(s): 倉重佑輝、柳井毅
  • Organizer: 第７回分子科学討論会
  • Place of Presentation: 京都府、京都テルサ
• [Presentation] 多参照波動関数理論で解く 光合成系IIマンガンクラスタの電子構造 (2013)
  • Author(s): 倉重佑輝
  • Organizer: 新学術領域研究「人工光合成」第2回公開シンポジウム特別セッション
  • Place of Presentation: 京都府、立命館 朱雀キャンパス
  • Invited
• [Presentation] Entangled quantum electronic wavefunctions of the Mn4CaO5 cluster in photosystem II (2013)
  • Author(s): Y. Kurashige
  • Organizer: The 51st Annual Meeting of the Biophysical Society of Japan
  • Place of Presentation: 京都府、国立京都国際会館
  • Invited
• [Presentation] 多核金属酵素・触媒の電子状態計算～光合成水分解反応を中心に～ (2013)
  • Author(s): 倉重佑輝、柳井毅
  • Organizer: TCCI 第3回実験化学との交流シンポジウム
  • Place of Presentation: 京都府、京都大学福井謙一記念研究センター
  • Invited
• [Presentation] Entangled quantum electronic wavefunctions of the Mn4CaO5 cluster in photosystem II (2013)
  • Author(s): Yuki Kurashige
  • Organizer: The 5th JCS International Symposium on Theoretical Chemistry
  • Place of Presentation: 奈良県、東大寺総合文化センター
  • Invited